The present invention relates to black-dyeing inks based on navy blue copper complex azo or copper complex formazan dyes, black-dyeing mixtures based on such dyes and novel dyes.
The inks on which the present invention is based are particularly suitable for printing paper, preferably by the ink-jet printing process, and for dyeing or printing fibre materials which contain nitrogen or hydroxyl groups, and give dyeings or prints which are distinguished by a high fastness to light.
The present invention therefore relates to black-dyeing aqueous inks comprising 20 to 95% by weight of at least one dye (A), together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the ink, and 1 to 40% by weight of a water-miscible organic solvent, based on the total weight of the ink, the dye (A) containing, as the colouring part of the molecule, one or more radicals of the formula (I), (II), (III) or (IV) 
the dye (B) containing, as the colouring part of the molecule, one or more mono- or disazo radicals containing sulfo groups or one or more radicals of the formula (V), (VI), (VII) or (VIII) 
and the dye (C) containing, as the colouring part of the molecule, one or more mono- or disazo radicals containing sulfo groups or one or more radicals of the abovementioned formula (V), (VI), (VII) or (VII) and one or more radicals of the abovementioned formula (I), (II), (III) or (IV), in which
(G)0-2 is 0 to 2 identical or different substituents from the group consisting of substituted or unsubstituted amino, hydroxyl and nitro,
L is substituted or unsubstituted amino,
R is halogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, carboxyl, nitro or cyano,
(V)0-2 is 0 to 2 identical or different substituents from the group consisting of halogen, C1-C4alkyl, C1-C4alkoxy, xcex2-sulfatoethylsulfonyl and sulfo,
(W)0-1 is an N-acyl radical, if any,
n is the number 0, 1, 2 or 3,
m is the number 1, 2 or 3 and
r and q are the number O or 1.
C1-C4alkyl R and V is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl, and in particular methyl.
C1-C4alkoxy R and V is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, preferably methoxy or ethoxy, and in particular methoxy.
Halogen R and V is, for example, fluorine, chlorine or bromine, preferably chlorine or bromine, and in particular chlorine.
C2-C4alkanoylamino R is, for example, acetylamino or propionylamino, in particular acetylamino.
R is preferably C1-C4alkyl, C1-C4alkoxy, hydroxyl, carboxyl, nitro or cyano, in particular C1-C4alkyl, C1-C4alkoxy, hydroxyl or carboxyl, and especially carboxyl.
V is preferably halogen, xcex2sulfatoethylsulfonyl or sulfo, in particular sulfo.
Substituted or unsubstituted amino G and L is, for example, amino, N-mono- or N,N-di- C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy, hydroxyl, sulfato or sulfo, or phenylamino or N-C1-C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, carboxyl or halogen, in particular amino or phenylamino.
An N-acyl radical W is, for example, C2-C4alkanoylamino, for example acetylamino or propionylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or sulfo, or a radical of the formula 
in which T1 and T2 independently of one another are fluorine or chlorine, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato, sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C1-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, carboxyl, C1-C4alkoxy, sulfato or sulfo, morpholino, phenylamino or N-C1-C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups.
q is preferably the number 1.
m is preferably the number 2 or 3, in particular 2.
If R is carboxyl, the sum of m+n is preferably 3 or 4, and in particular 3.
Inks according to the invention which are preferred are those which contain a radical of the formula (IV) in which
q is the number 1,
n is the number 0 and
m is the number 2 or 3.
The sulfo groups of the dyes (A), (B) and (C) in the inks according to the invention are either in the form of the free sulfonic acid or, preferably, in the salt form thereof, for example as the sodium, lithium, potassium or ammonium salt or as the salt of an organic amine, for example as the triethanolammonium salt.
The dyes (A), (B) and (C) in the inks according to the invention contain no further colouring molecular moieties in addition to the colouring molecular moieties mentioned.
The dye (A) in the inks according to the invention preferably contains, as the colouring molecular moiety (chromophore), one or two radicals of the formula (I), (II), (III) or (IV).
If the dye (A) contains a radical of the formula (I), (II), (III) or (IV), a non-chromophoric radical is bonded to this radical via the free valency drawn in the formulae (I), (II), (III) and (IV).
Examples of a non-chromophoric radical are the following:
C2-C6alkanoylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfo, carboxyl or C1-C4alkoxy, which can in its turn be substituted in the alkyl moiety by carboxyl, for example acetylamino, hydroxyacetylamino, methoxyacetylamino, carboxymethylenoxyacetylamino, propionylamino or xcex2-carboxypropionylamino; N-C1-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfo, carboxyl or C1-C4alkoxy, for example 3-sulfopropylamino or 4-sulfobutylamino; benzoylamino which is unsubstituted or substituted in the phenyl moiety by hydroxyl, sulfo, halogen, C1-C4alkyl or C1-C4alkoxy; C2-C6alkoxycarbonylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, C1-C4alkyl or C1-C4alkoxy; phenoxycarbonylamino which is unsubstituted or substituted in the phenyl moiety by hydroxyl, C1-C4alkyl or C1-C4alkoxy; phenylsulfonylamino which is unsubstituted or substituted in the phenyl moiety by C1-C4alkyl or C2-C4alkanoylamino, or C1-C4alkylsulfonylamino, for example methyl- or ethylsulfonylamino, or a radical of the formula 
xe2x80x83in which T3 and T4 independently of one another are a substituent which is not fibre-reacted, for example C1-C4alkoxy, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato, sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C1-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxyl, carboxyl, C1-C4alkoxy, sulfato or sulfo, morpholino, phenylamino or N-C1-C4alkyl-N-phenylamino, which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy, and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups.
Non-chromophoric radicals which are bonded via the free valency in the formula (I), (II), (III) or (IV) are also fibre-reactive radicals.
Fibre-reactive radicals are, for example, an alkanoyl or alkylsulfonyl radical substituted by an atom which can be split off or a group which can be split off, an alkenoyl or alkenesulfonyl radical which is unsubstituted or substituted by an atom which can be split off or a group which can be split off, or an alkenoyl or alkenesulfonyl radical which contains a vinyl group. The alkanoyl, alkylsulfonyl and alkenesulfonyl radicals mentioned as a rule contain 2 to 8 carbon atoms and the alkenoyl radicals as a rule contain 3 to 8 carbon atoms. These radicals are also radicals which contain carbo- or heterocyclic 4-, 5- or 6-membered rings and are substituted by an atom which can be split off or a group which can be split off. Heterocyclic radicals are, for example, those which contain at least one substituent which can be split off bonded to a heterocyclic radical; inter alia, those which contain at least one reactive substituent bonded to a 5- or 6-membered heterocyclic ring, such as to a monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to such a ring system which has one or more fused-on aromatic rings, such as a quinoline, phthalazine, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system.
Atoms which can be split off and groups which can be split off are, in addition to others, for example, halogen, such as fluorine, chlorine or bromine, ammonium, including hydrozinium, sulfato, thiosulfato, phosphato, acetoxy, propionoxy, azido, carboxypyridinium or thiocyanato.
The fibre-reactive radical and the chromophore of the formula (I), (II), (III) or (IV) can be bonded to one another by a bridge member. Bridge members are, in addition to the direct bond or, for example, an amino group, the most diverse radicals. The bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; the bridge member can furthermore also be composed of different such radicals. The bridge member as a rule contains at least one functional group, for example the carbonyl, sulfonyl, carbonylamino, sulfonylamino or the amino group, it being possible for the amino group to be further substituted by C1-C4alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano, C1-C4alkoxy, C1-C4alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato. An aliphatic radical is, for example, an alkylene radical having 1 to 7 carbon atoms or branched isomers thereof. The carbon chain of the alkylene radical can be interrupted by a heteroatom, for example an oxygen atom. An aromatic radical is, for example, a phenylene radical, which can be substituted by C1-C4alkyl, for example methyl or ethyl, C1-C4alkoxy, for example methoxy or ethoxy, halogen, for example fluorine, bromine or, in particular, chlorine, carboxyl or sulfo, and a heterocyclic radical is, for example, a piperazine or a triazine radical, it being possible for the triazine radical to contain a substituent which can be split off, for example fluorine or chlorine.
Such fibre-reactive radicals are known per se and a large number are described, for example, in Venkataraman xe2x80x9cThe Chemistry of Synthetic Dyesxe2x80x9d Volume 6, Pages 1-209, Academic Press, New York, London 1972 or in U.S. Pat. No. 5,684,138.
The dyes (A) which comprise a chromophore of the formula (I), (II), (III) or (IV) are known or can be prepared analogously to known dyes.
Suitable dyes (A) which comprise a chromophore of the formula (IV) are, for example, C.I. Reactive Blue 52, 70, 83, 84, 104, 157, 160, 182, 202, 209, 212, 218, 220, 221, 226, 228 and 232 and the dyes of the formulae (IV.1), (IV.2), (IV.3), (IV.4), (IV.5), (IV.6), (IV.7) and (IV.8) 
preferably C.I. Reactive Blue 52 and 182 and the dyes of the formulae (IV.1), (IV.2), (IV.3), (IV.4), (IV.5), (IV.6), (IV.7) and (IV.8), and in particular the dyes of the formulae (IV.1), (IV.2), (IV.3), (IV.4), (IV.5), (IV.6), (IV.7) and (IV.8).
Suitable dyes which comprise a chromophore of the formula (IV) and contain a fibre-reactive radical are furthermore described, for example, in GB-A-2 148 921, U.S. Pat. No. 4,994,562, U.S. Pat. No. 5,021,557, U.S. Pat. No. 5,023,274, U.S. Pat. No. 5,076,811, U.S. Pat. No. 5,112,958 and U.S. Pat. No. 5,371,200.
If the dye (A) contains two radicals of the formula (I), (II), (III) or (IV), these radicals are bonded to one another by a bridge member, in each case via the free valency in the formulae (I), (II), (III) and (IV). Bridge members are the most diverse radicals. The bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; the bridge member can furthermore also be composed of different such radicals. The bridge member as a rule contains at least two functional groups, for example the carbonyl, sulfonyl, carbonylamino, sulfonylamino or the amino group, it being possible for the amino group to be further substituted by C1-C4alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano, C1-C4alkoxy, C1-C4alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato. An aliphatic radical is, for example, an alkylene radical having 1 to 10 carbon atoms or branched isomers thereof. The carbon chain of the alkylene radical can be interrupted by a heteroatom, for example an oxygen atom. The term aliphatic radical also includes cycloaliphatic radicals. An aromatic radical is, for example, a naphthylene radical, the radical of a diphenyl or stilbene, or, in particular, a phenylene radical, which can be substituted by C1-C4alkyl, for example methyl or ethyl, C1-C4alkoxy, for example methoxy or ethoxy, halogen, for example fluorine, bromine or, in particular, chlorine, carboxyl or sulfo, and a heterocyclic radical is, for example, a triazine radical.
The dyes (A) which comprise two chromophore radicals of the formula (I), (II), (III) or (IV) bonded to one another via a bridge member are known or can be prepared analogously to known dyes. A suitable dye is, for example, the dye of the formula (IV.9) 
Suitable dyes (A) which comporise two chromophore radicals of the formula (IV) bonded to one another via a bridge member are furthermore described, for example, in GB-A-1 389 053, GB-A-2 148 921, U.S. Pat. No. 5,232,462, U.S. Pat. No. 5,410,041 and U.S. Pat. No. 5,684,138.
The chromophore of the formula (I), (II) or (III) contained in the dye (A) is preferably one or two radicals of the formula (I.1), (I.2), (I.3), (I.4), (I.5), (II.1), (II.2), (II.3) or (III.1) 
The chromophore contained in the dye (C) is preferably a mono- or disazo radical containing sulfo groups or a radical of the formula (V), (VI), (VII) or (VII) and a radical of the formula (I), (II), (III) or (IV).
The mono- or disazo radicals and the radicals of the formulae (V), (VI), (VII) and (VII) on which the dyes (B) and (C) of the inks according to the invention are based are, for example, yellow-, orange-, red- or claret- to violet-colouring dye radicals.
Suitable dye radicals of the formula (V), (VI), (VII) and (VII) are, for example, those of the formulae (V.1), (V.2), (V.3), (V.4), (V.5), (V.6), (V.7), (VI.1), (VII.1), (VIII.1), (VIII.2) and (VIII.3) 
The chromophore of the formula (IV) contained in the dye (A) is preferably one or two radicals of the formula (IVa), (IVb) or (IVc) 
in particular of the formula (IVb) or (IVc).
The chromophore contained in the dye (B) is preferably one or two mono- or disazo radicals containing sulfo groups or one or two radicals of the formula (V), (VI), (VII) or (VIII). 
Examples of substituents in the mono- or disazo radical are the following:
alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl, sulfo or sulfato; phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo; acylamino groups having 1 to 8 carbon atoms, in particular such alkanoylamino groups, for example acetylamino or propionylamino; benzoylamino which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or sulfo; phenylamino which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or sulfo; N,N-di-xcex2-hydroxyethylamino; N,N-di-xcex2-sulfatoethylamino; sulfobenzylamino; N,N-disulfobenzylamino; alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl; alkylsulfonyl having 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; amino; cyano; halogen, such as fluorine, chlorine or bromine; carbamoyl; N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl; N-mono- or N,N-dialkylsulfamoyl having in each case 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, it being possible for the alkyl radicals to be further substituted, for example by hydroxyl or sulfo; N-(xcex2-hydroxyethyl)-sulfamoyl; N,N-di-(xcex2-hydroxyethyl)-sulfamoyl; N-phenylsulfamoyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo; ureido; hydroxyl; carboxyl; sulfomethyl or sulfo, and the fibre-reactive radicals described above.
The mono- or disazo radicals containing sulfo groups in the dyes (B) and (C) of the inks according to the invention are preferably those of the formula (2) or (3)
Dxe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)uxe2x80x94Kxe2x80x94xe2x80x83xe2x80x83(2) 
or
xe2x80x94Dxe2x80x94Nxe2x95x90Nxe2x80x94(Mxe2x80x94Nxe2x95x90N)uxe2x80x94Kxe2x80x83xe2x80x83(3),
in which D is the radical of a diazo component of the benzene or naphthalene series, M is the radical of a middle component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide series and u is the number 0 or 1, where D, M and K can carry substituents customary in azo dyes, for example C1-C4alkyl or C1-C4alkoxy which are unsubstituted or further substituted by hydroxyl, sulfo or sulfato, halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C2-C4alkanoylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or sulfo, phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl or sulfo, and fibre-reactive radicals.
If u is the number 1, D, M and K are preferably radicals of a diazo, middle and coupling component of the benzene or naphthalene series, and in particular of the benzene series.
A radical of the formula (2) or (3) in the dye (B) has bonded to it, via the free valency drawn in the formula (2) or (3), a non-chromophoric substituent, for example one of the substituents mentioned above for mono- or disazo radicals, or a radical of the formula 
in which T3 and T4 independently of one another are a substituent which is not fibre-reactive, for example C1-C4alkoxy, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato, sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alky moiety by hydroxyl, carboxyl, C1-C4alkoxy, sulfato or sulfo, morpholino, phenylamino or N-C1-C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy, and in which the alkyl is unsubstituted or substituted by hydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups.
The radicals mentioned can also satisfy the free valency of the dye (B) which comprises a chromophore radical of the formula (V), (VI), (VII) or (VII).
The dyes (B) which comprise a chromophore of the formula (2), (3), (V), (VI), (VII) or (VII) are known or can be prepared analogously to known dyes.
Suitable dyes (B) which comprise a chromophore of the formula (2) are, for example, the dyes of the formulae (2.1), (2.2), (2,3) and (2.4) 
Two radicals of the formula (2), (3), (V), (VI), (VII) or (VIII), contained in the dye (B) are bonded to one another by a bridge member, in each case via the free valency. Bridge members are, for example, those radicals which have already been described above in connection with the dye (A) containing two radicals of the formula (I), (II), (III) or (IV).
The dyes (B) which comprise two chromophore radicals of the formula (2), (3), (V), (VI), (VII) or (VIII) bonded to one another via a bridge member are known or can be prepared analogously to known dyes.
Suitable dyes (B) which comprise two chromophore radicals of the formula (2) bonded to one another via a bridge member are, for example, the dyes of the formulae (2.5), (2.6) and (2.7) 
The dye radicals in the dye (C) are bonded to one another via a bridge member, in each case via the free valency in the formula (I), (II), (III) or (IV) and the formula (2), (3), (V), (VI), (VII) or (VIII). Bridge members are, for example, those radicals which have already been described above in connection with the dye (A) containing two radicals of the formula (I), (II), (III) or (IV).
The dyes (C) on which the inks according to the invention are based are known in some cases or can be prepared analogously to known dyes. The present invention also relates to the novel dyes (C) on which the inks according to the invention are based.
Suitable dyes (C) and dyes (B) which comprise two chromophore radicals bonded to one another via a bridge member are furthermore described, for example, in U.S. Pat. No. 5,232,462, U.S. Pat. No. 5,243,033, U.S. Pat. No. 5,410,041 and U.S. Pat. No. 5,684,138.
The radicals of the formulae (2) and (3) each contain at least one sulfo group, preferably 1 to 4 sulfo groups, in particular 1 to 3 sulfo groups, and especially 2 sulfo groups.
The dye (C) preferably contains, as the chromophore, a radical of the formula (I), (II), (III), (IVa), (IVb) or (IVc), in particular (I.1), (I.2), (I.3), (I.4), (I.5), (II.1), (II.2), (II.3), (II.1), (III.1), (IVb) or (IVc).
The radicals of the formulae (2) and (3) are preferably radicals of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j), (4k), (41), (4m), (4n), (4o), (4p), (4q) or (4r) 
in which (R1)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, halogen, carboxyl and sulfo and Z is vinyl or a radical xe2x80x94CH2xe2x80x94CH2xe2x80x94U and U is a leaving group, 
in which (R1)0-3 is as defined above, 
in which (R1)0-3 is as defined above, 
in which (R2)0-4 is 0 to 4 identical or different substituents from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, amino, C2-C4alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C1-C4alkylsulfonylamino and sulfo and Z is as defined above, 
in which R3 is C2-C4alkanoyl or benzoyl, 
in which R3 is as defined above, 
in which (R4)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo, 
in which (R4)0-3 is as defined above, 
in which R5 and R7 independently of one another are hydrogen, C1-C4alkyl or phenyl, and R6 is hydrogen, cyano, carbamoyl or sulfomethyl, 
in which (R8)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo; and Z is as defined above, 
in which (R9)0-2 is 0 to 2 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo; and Z is as defined above, 
in which
(R1)0-3, (R2)0-3, (R4)0-3 and Z are each as defined above and (R1xe2x80x2)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo.
C1-C4alkyl R1, R1xe2x80x2, R2, R4, R5, R7, R8 and R9 independently of one another are, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl, and in particular methyl.
C1-C4alkoxy R1, R1xe2x80x2, R2, R4, R8 and R9 independently of one another are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, preferably methoxy or ethoxy, and in particular methoxy. C1-C4alkoxy R2 is unsubstituted or substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy, for example radicals of the formula xe2x80x94Oxe2x80x94CH2CH2xe2x80x94OH or xe2x80x94Oxe2x80x94CH2CH2xe2x80x94OCH3.
Halogen R1, R1xe2x80x2, R2, R4, R8 and R9 independently of one another are, for example, fluorine, chlorine or bromine, preferably chlorine or bromine, and in particular chlorine.
C2-C4alkanoylamino R1 and R2 independently of one another are, for example, acetylamino or propionylamino, in particular acetylamino.
C2-C4-alkanoyl R3 is, for example, acetyl, propionyl or butyryl, preferably acetyl or propionyl, and in particular acetyl.
C1-C4alkylsulfonylamino R2 is, for example, methylsulfonylamino or ethylsulfonylamino, in particular methylsulfonylamino.
The leaving group U is, for example, xe2x80x94Cl, xe2x80x94Br, xe2x80x94F, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OPO3H2, xe2x80x94OCOxe2x80x94C6H5, xe2x80x94OSO2xe2x80x94C1-C4alkyl or xe2x80x94OSO2xe2x80x94N(C1-C4alkyl)2. Preferably, U is a group of the formula xe2x80x94Cl, xe2x80x94OSO3H, xe2x80x94SSO3H, xe2x80x94OCOxe2x80x94CH3, xe2x80x94OCOxe2x80x94C6H5 or xe2x80x94OPO3H2, in particular xe2x80x94Cl or xe2x80x94OSO3H, and particularly preferably xe2x80x94OSO3H.
The radicals of the formulae (4a) to (4r) are preferably radicals which contain no fibre-reactive group. Radicals which are of particular interest are those of the formulae (4a), (4d), (4e), (4i), (4k), (4n), (4o), (4p), (4q) and (4r), in particular the radicals of the formulae (4a), (4d), (4e), (4o), (4p), (4q) and (4r). The radicals of the formulae (4e), (4o), (4p) and (4q) are of special interest.
Preferred inks are those in which the dye (A) has the formula (5) 
in which
R10, R11, R12 and R13 independently of one another are hydrogen or substituted or unsubstituted C1-C4alkyl,
B1 is an aliphatic or aromatic bridge member,
F1 and F2 independently of one another are a radical of the formula (I), (II), (III) or (IV), and
X1 and X2 independently of one another are halogen, hydroxyl, C1-C4alkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono- or N,N-di-C1-C6alkylamino which are unsubstituted or substituted in the alkyl moiety, C5-C7-cycloalkylamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-C1-C4alkyl-N-phenyl- or N-C1-C4alkyl-N-naphthylamino which are unsubstituted or substituted in the aryl moiety, benzylamino which is unsubstituted or substituted in the phenyl moiety, morpholino or piperidin-1-yl.
Preferred inks are those in which the dye (B) has the formula (6) 
and the dye (C) has the formula (7) 
in which
R14, R15, R16, R17, R18, R19, R20 and R21 independently of one another are hydrogen or substituted or unsubstituted C1-C4alkyl,
B2 and B3 independently of one another are an aliphatic or aromatic bridge member,
A1, A2 and A3 independently of one another are a mono- or disazo radical containing sulfo groups or a radical of the formula (V), (VI) or (VII),
F3 is a radical of the formula (I), (II), (III) or (IV) and
X3, X4, X5 and X6 independently of one another are halogen, hydroxyl, C1-C4alkoxy which is unsubstituted or substituted in the alkyl moiety, phenoxy which is unsubstituted or substituted in the phenyl ring, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety, phenylthio which is unsubstituted or substituted in the phenyl ring, amino, N-mono- or N,N-di-C1-C6alkylamino which are unsubstituted or substituted in the alkyl moiety, C5-C7-cycloalkylamino which is unsubstituted or substituted in the cycloalkyl ring, phenyl- or naphthylamino or N-C1-C4alkyl-N-phenyl- or N-C1-C4alkyl-N-naphthylamino which are unsubstituted or substituted in the aryl moiety, benzylarhino which is unsubstituted or substituted in the phenyl moiety, morpholino or piperidin-1-yl.
Alkyl radicals R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20 and R21 are straight-chain or branched. The alkyl radicals can be further substituted, for example by hydroxyl, sulfo, sulfato, cyano or carboxyl. Examples are the following radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, and the corresponding radicals substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred substituents are hydroxyl, sulfo, sulfato or carboxyl, in particular hydroxyl or sulfato, and preferably hydroxyl.
Aliphatic bridge members B1, B2 and B3 are, for example, a C2-C12alkylene radical, in particular a C2-C6alkylene radical, which can be interrupted by 1, 2 or 3 members from the group consisting of xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 or, in particular, xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred substituents of the alkylene radicals mentioned for B1, B2 and B3 are hydroxyl, sulfo or sulfato, in particular hydroxyl.
Aliphatic bridge members B1, B2 and B3 are furthermore, for example, C5-C9-cycloalkylene radicals, such as, in particular, cyclohexylene radicals. The cycloalkylene radicals mentioned can be unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl, in particular by C1-C4alkyl. Aliphatic bridge members B1, B2 and B3 are furthermore methylene-cyclohexylene, ethylene-cyclohexylene or methylene-cyclohexylene-methylene radicals which are unsubstituted or substituted in the cyclohexylene ring by C1-C4alkyl, in particular methyl.
The radicals of the formulae xe2x80x94N(R11)xe2x80x94B1xe2x80x94N(R12)xe2x80x94, xe2x80x94N(R15)xe2x80x94B2xe2x80x94N(R16)xe2x80x94 and xe2x80x94N(R19)xe2x80x94B3xe2x80x94N(R20)xe2x80x94 can also be, for example, a radical of the formula 
or 
in which alk is, for example, C1-C4alkylene, for example ethylene.
Aromatic bridge members B1, B2 and B3 are C1-C6alkylenephenylene, such as methylenephenylene, C1-C4alkylenephenylene-C1-C4alkylene, for example methylenephenylenemethylene, or phenylene which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl, or a radical of the formula 
in which the benzene rings I and II are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl and L is the direct bond or a C2-C10alkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms,.or L is a bridge member of the formula xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Nxe2x95x90Nxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94SO2xe2x80x94 xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94SO2xe2x80x94. Aromatic bridge members B1, B2 and B3 are preferably phenylene, which can be substituted as mentioned above. Preferably, the aromatic bridge members B1, B2 and B3 are unsubstituted or substituted by sulfo. B1, B2 and B3 are preferably a C2-C12alkylene radical, which can be interrupted by 1, 2 or 3 members from the group consisting of xe2x80x94NHxe2x80x94, xe2x80x94N(CH3)xe2x80x94 or xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl; or a C5-C9cycloalkylene radical, C1-C6alkylenephenylene radical or phenylene radical which are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl; or B1, B2 and B3 are a radical of the formula (8), in which the benzene rings I and II are unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl and L is the direct bond or a C2-C10alkylene radical, which can be interrupted by 1, 2 or 3 oxygen atoms, or L is a bridge member of the formula xe2x80x94CHxe2x95x90CHxe2x80x94, xe2x80x94Nxe2x95x90Nxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94NHxe2x80x94 SO2xe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94SO2xe2x80x94 ist; or the radicals of the formulae xe2x80x94N(R11)xe2x80x94B1xe2x80x94N(R12)xe2x80x94, xe2x80x94N(R15)xe2x80x94B2xe2x80x94N(R16)xe2x80x94 and xe2x80x94N(R19)xe2x80x94B1xe2x80x94N(R20)xe2x80x94 are a piperazine radical of the formula 
B1, B2 and B3 are particularly preferably a C2-C12alkylene radical, which can be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl, or
a phenylene radical which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo, halogen or carboxyl.
B1, B2 and B3 are especially preferably a C2-C12alkylene radical, in particular a C2-C6alkylene radical, which can be interrupted by 1, 2 or 3 members xe2x80x94Oxe2x80x94 and is unsubstituted or substituted by hydroxyl or sulfato.
Bridge members B1, B2 and B3 of particular interest are C2-C6alkylene radicals, in particular those of the formula xe2x80x94CH2xe2x80x94CH(R22)xe2x80x94 or xe2x80x94(R22)xe2x80x94CHxe2x80x94CH2xe2x80x94, in which R22 is C1-C4alkyl, in particular methyl.
Halogen X1, X2, X3, X4, X5 and X6 independently of one another are, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine, and in particular chlorine.
C1-C4alkoxy X1, X2, X3, X4, X5 and X6 independently of one another are, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, in particular methoxy or ethoxy. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C1-C4alkoxy, for example methoxy or ethoxy, hydroxyl, sulfo or carboxyl.
C1-C4alkylthio X1, X2, X3, X4, X5 and X6 independently of one another are, for example, methylthio, ethylthio, propylthio, isopropylthio or butylthio. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C1-C4alkoxy, for example methoxy or ethoxy; hydroxyl; sulfo or carboxyl. The radicals substituted in the alkyl moiety by one or two radicals from the group consisting of hydroxyl, sulfo and carboxyl are preferred.
N-mono- or N,N-di-C1-C6alkylamino, preferably N-mono- or N,N-di-C1-C4alkylamino, X1, X2, X3, X4, X5 and X6 independently of one another are, for example, N-methylamino, N-ethylamino, N-propylamino, N-butylamino, N-hexylamino, N,N-dimethylamino or N,N-di-ethylamino. The radicals mentioned are unsubstituted or substituted in the alkyl moiety, for example by C2-C4alkanoylamino, for example acetylamino or propionylamino; C1-C4alkoxy, for example methoxy or ethoxy; hydroxyl; sulfo; sulfato; carboxyl; carbamoyl; sulfamoyl or xcex2-sulfatoethylsulfonyl. The radicals mentioned are uninterrupted or interrupted in the alkyl moiety by oxygen. Examples of radicals which are substituted in the alkyl moiety and which are interrupted in the alkyl moiety by oxygen are N-xcex2-hydroxyethylamino, N,N-di-xcex2-hydroxyethylamino, N-2-(xcex2-hydroxyethoxy)-ethylamino, N-2-[2-(xcex2-hydroxyethoxy)ethoxy]ethylamino, N-xcex2-sulfatoethylamino, N-xcex2-sulfoethylamino, N-carboxymethylamino, N-xcex2-carboxyethylamino, N-xcex1,xcex2-dicarboxyethylamino, N-xcex1,xcex3-dicarboxypropylamino, N-ethyl-N-xcex2-hydroxyethylamino and N-methyl-N-xcex2-hydroxyethylamino. The radicals which are substituted in the alkyl moiety by hydroxyl; sulfo; sulfato; carboxyl or carbamoyl are preferred.
C5-C7cycloalkylamino X1, X2, X3, X4, X5 and X6 independently of one another can include both the unsubstituted radicals and the radicals which are substituted in the cycloalkyl ring, for example by C1-C4alkyl, for example methyl or ethyl, in particular methyl, or carboxyl. Preferred such radicals are the corresponding cyclohexyl radicals.
Phenylamino or N-C1-C4alkyl-N-phenylamino, preferably phenylamino, X1, X2, X3, X4, X5 and X6 independently of one another can include both the unsubstituted radicals and the radicals which are substituted in the phenyl ring, for example by C1-C4alkyl, for example methyl or ethyl, which is unsubstituted or further substituted, for example by carboxyl; C1-C4alkoxy, for example methoxy or ethoxy; carboxyl; carbamoyl; N-C1-C4alkylcarbamoyl, which is unsubstituted or further substituted in the alkyl moiety, for example by carboxyl, for example N-carboxymethylcarbamoyl; sulfo or halogen, for example chlorine or bromine. The substituted radicals, preferably the radicals substituted by carboxyl, carboxymethyl, N-carboxymethylcarbamoyl or sulfo, in particular sulfo, are preferred.
Naphthylamino or N-C1-C4alkyl-N-naphthylamino, preferably naphthylamino, X1, X2, X3, X4, X5 and X6 independently of one another can include both the unsubstituted radicals and the radicals substituted in the naphthyl ring, for example by sulfo. The radicals substituted by 1 to 3, in particular 2 to 3, sulfo groups are preferred.
Benzylamino X1, X2, X3, X4, X5 and X6 which are unsubstituted or substituted in the phenyl moiety independently of one another can include both the unsubstituted radicals and the radicals substituted in the phenyl ring, for example by C1-C4alkyl, for example methyl or ethyl; C1-C4alkoxy, for example methoxy or ethoxy; carboxyl; sulfo or halogen, for example chlorine or bromine. The radicals substituted in the phenyl ring by carboxyl are preferred.
X1, X2, X3, X4, X5 and X6 are preferably halogen, C1-C4alkoxy, or alkylthio which are unsubstituted or substituted in the alkyl moiety by C1-C4alkoxy, hydroxyl, sulfo or carboxyl, N-mono, or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by C2-C4alkanoylamino, C1-C4alkoxy, hydroxyl, sulfo, sulfato, carboxyl, carbamoyl or sulfamoyl, C5-C7-cycloalkylamino which is unsubstituted or substituted by C1-C4alkyl or carboxyl, phenylamino or N-C1-C4alkyl-N-phenylamino which are unsubstituted or substituted in the phenyl moiety by C1-C4alkyl, which is unsubstituted or further substituted by carboxyl, C1-C4alkoxy, carboxyl, carbamoyl, N-C1-C4alkylcarbamoyl, which is unsubstituted or further substituted in the alkyl moiety by carboxyl, sulfo or halogen, naphthylamino which is substituted in the aryl moiety by sulfo, or benzylamino which is unsubstituted or substituted in the phenyl moiety by C1-C4alkyl, C1-C4alkoxy, carboxyl, sulfo or halogen.
X1, X2, X3, X4, X5 and X6 particularly preferably independently of one another are halogen, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfo or carboxyl, in particular sulfo or carboxyl, N-mono- or N,N-di-C1-C4alkylamino which is unsubstituted or substituted in the alkyl moiety by C2-C4alkanoylamino, C1-C4alkoxy, hydroxyl, sulfo, sulfato, carboxyl or carbamoyl, in particular hydroxyl, sulfo or carboxyl, or morpholino.
R10, R13, R14, R17, R18 and R21 are preferably hydrogen or C1-C4alkyl, in particular hydrogen.
R11, R12, R15, R16, R19 and R20 are preferably hydrogen or C1-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato or carboxyl, preferably hydrogen or C1-C4alkyl, and in particular hydrogen.
The radicals F1 and F2 in the dye of the formula (5) can be different or identical. Preferably, the radicals F1 and F2 are identical.
The radicals A1 and A2 in the dye of the formula (6) can be different or identical. Preferably, the radicals A1 and A2 are identical.
The radicals X1 and X2 in the dye of the formula (5) can be different or identical. Preferably, the radicals X1 and X2 are identical.
The radicals X3 and X4 in the dye of the formula (6) can be different or identical. Preferably, the radicals X3 and X4 are identical.
The radicals X5 and X6 in the dye of the formula (7) can be different or identical. Preferably, the radicals X5 and X6 are identical.
Preferred inks are those in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7), in which R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, B1, B2, B3, F1, F2, F3, A1, A2, A3, X1, X2, X3, X4, X5 and X6 are as defined and preferred above under formulae (5), (6) and (7).
Particularly preferred inks are those in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7), in which
R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20 and R21 are hydrogen, B1, B2 and B3 independently of one another are a radical of the formula xe2x80x94CH2xe2x80x94CH(R22)xe2x80x94 or xe2x80x94(R22)xe2x80x94CHxe2x80x94CH2xe2x80x94, in which R22 is C1-C4alkyl, in particular methyl,
F1, F2 and F3 independently of one another are a radical of the formula (I), (II), (III), (IVa), (IVb) or (IVc), in particular (I.1), (I.2), (I.3), (I.4), (I.5), (II.1), (II.2), (II.3), (III.1), (IVb) or (IVc), A1, A2 and A3 independently of one another are a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j), (4k), (41), (4m), (4n), (40), (4p), preferably (4a), (4d), (4e), (4o), (4p), (4q), (4r), (V), (VI) or (VII), and in particular (4e), (4o), (4p), (4q), (V), (VI) or (VII), which contain no fibre-reactive substituents, and
X1, X2, X3, X4, X5 and X6 independently of one another are halogen, C1-C4alkylthio which is unsubstituted or substituted in the alkyl moiety by hydroxyl, sulfo or carboxyl, in particular sulfo or carboxyl, N-mono- or N,N-di-C1-C4alkylamino which are unsubstituted or substituted in the alkyl moiety by C2-C4alkanoylamino, C1-C4alkoxy, hydroxyl, sulfo, sulfato, carboxyl or carbamoyl, in particular hydroxyl, sulfo or carboxyl, or morpholino.
A particularly preferred embodiment of the present invention comprises inks which comprise at least one dye (A) of the formula (5) together with at least one dye (C) of the formula (7), in which
R10, R11, R12, R13, R18, R19, R20, R21, B1, B3, F1, F2, F3, A3, X1, X2, X5 and X6 are as defined and preferred above.
Further suitable dyes (C) for the inks according to the invention have the formula (9) 
in which
R23 is as defined and preferred for R10, R13, R14, R17, R18 and R21,
R24 and R25 independently of one another are as defined and preferred for R11, R12, R15, R16,
R19 and R20,
B4 is as defined and preferred for B1, B2 and B3,
A4 is a radical of the formula (VII),
F4 is as defined and preferred for F1, F2 and F3 and
X7 is as defined and preferred for X1, X2, X3, X4, X5 and X6.
The inks according to the invention preferably comprise 30 to 95% by weight of at least one dye (A) together with 5 to 70% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of dyes (A), (B) and (C) in the ink.
If the ink according to the invention comprises at least one dye (A) together with at least one dye (B), the dye (A) is present, for example, in an amount of 60 to 95% by weight, preferably 70 to 95% by weight, in particular 75 to 90% by weight, and the dye (B) is present, for example, in an amount of 5 to 40% by weight, preferably 5 to 30% by weight, and in particular 10 to 25% by weight, based on the total weight of the dyes (A) and (B) in the ink.
If the ink according to the invention comprises at least one dye (A) together with at least one dye (C), the dye (A) is present, for example, in an amount of 25 to 90% by weight, preferably 30 to 80% by weight, and in particular 30 to 70% by weight, and the dye (C) is present, for example, in an amount of 10 to 75% by weight, preferably 20 to 70% by weight, and in particular 30 to 70% by weight, based on the total weight of the dyes (A) and (C) in the ink.
The inks according to the invention can comprise further dyes for shading, in addition to the abovementioned dyes. Preferably, the inks comprise no substantial amounts of a further dye which does not fall under the definition according to the claims of the dyes in the inks according to the invention. xe2x80x9cSubstantial amountsxe2x80x9d in this connection is to be understood as meaning, for example, amounts of more than 5% by weight, based on the total weight of the dyes (A), (B) and (C) in the ink.
The dyes used in the inks according to the invention should preferably have a low salt content, i.e. comprise a total content of salts of less than 0.5% by weight, based on the weight of the dyes. Dyes which have relatively high salt content due to their preparation and/or the subsequent addition of diluents can be desalinated, for example, by membrane separation processes, such as ultrafiltration, reverse osmosis or dialysis.
The inks preferably comprise a total content of dyes of 1 to 35% by weight, in particular 1 to 30% by weight, and preferably 1 to 20% by weight, based on the total weight of ink. A limit of 2.5% by weight, in particular 5% by weight, and preferably 7.5% by weight, is preferred here as the lower limit.
Those inks which have a viscosity of 1 to 40 mPas (millipascal-seconds) are preferred.
The inks comprise water-miscible solvents in an amount of 1 to 40% by weight, for example C1-C4 alcohols, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or isobutanol; amides, for example dimethylformamide or dimethylacetamide, ketones or ketone alcohols, for example acetone or diacetone alcohol; ethers for example tetrahydrofuran or dioxane; nitrogen-containing heterocyclic compounds, for example N-methyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidone, polyalkylene glycols, for example polyethylene glycol or polypropylene glycol; C2-C6alkylene glycols and thioglycols, for example ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol and diethylene glycol; further polyols, for example glycerol or 1,2,6-hexanetriol; and C1-C4alkyl ethers of polyhydric alcohols, for example 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol or 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone, diethylene glycol, glycerol or, in particular, 1,2-propylene glycol, preferably in an amount of 2 to 30% by weight, in particular 5 to 30% by weight, and especially 10 to 25% by weight, based on the total weight of the ink.
The inks can furthermore also comprise solubilizing agents,for example xcex5-caprolactam.
The inks can comprise thickeners of natural or synthetic origin, inter alia for the purpose of adjusting the viscosity.
Examples of thickeners are commercially available alginate thickeners, starch ethers or carob bean flower ethers, in particular sodium alginate, by itself or as a mixture with modified cellulose, for example methyl-, ethyl-, carboxymethyl-, hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- or hydroxypropylmethylcellulose, in particular with preferably 20 to 25% by weight of carboxymethylcellulose. Synthetic thickeners are furthermore, for example, those based on poly(meth)acrylic acids or poly(meth)acrylamides.
The inks comprise such thickeners, for example, in an amount of 0.01 to 2% by weight, in particular 0.01 to 1% by weight, and preferably 0.01 to 0.5% by weight, based on the total weight of the ink.
The inks can furthermore comprise buffer substances, for example borax, borate, phosphate, polyphosphate or citrate. Examples are borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium tripolyphosphate, sodium pentaphosphate and sodium citrate. They are used, in particular, in amounts of 0.1 to 3% by weight, preferably 0.1 to 1% by weight, based on the total weight of the ink, in order to establish a pH of, for example, 4 to 10, preferably 5 to 8.
The inks can comprise surfactants or humectants as further additives.
Surfactants are the commercially available anionic or nonionic surfactants. Humectants are, for example, urea, glycerol, propylene glycol or a mixture of sodium lactate (advantageously in the form of a 50 to 60% aqueous solution) and glycerol and/or propylene glycol in amounts of preferably 0.1 to 30% by weight, in particular 2 to 30% by weight, in the inks according to the invention.
If desired, the inks can also comprise acid donors, such as butyrolactone or sodium hydrogen phosphate, preservatives, substances which inhibit fungal and/or bacterial growth, foam suppressants, sequestering agents, emulsifiers, water-insoluble solvents, oxidizing agents or de-aerating agents.
Preservatives are, in particular, formaldehyde-releasing agents, for example paraformaldehyde and trioxane, in particular aqueous, approximately 30 to 40% by weight formaldehyde solutions, sequestering agents are, for example, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, and in particular sodium polymetaphosphate, especially sodium hexametaphosphate, emulsifiers are, in particular, adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide, water-insoluble solvents are high-boiling saturated hydrocarbons, in particular paraffins with a boiling range from about 160 to 210xc2x0 C. (so-called white spirits) oxidizing agents are, for example, an aromatic nitro compound, in particular an aromatic mono- or dinitrocarboxylic acid or -sulfonic acid, which may be present as an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid, and de-aerating agents are, for example, high-boiling solvents, in particular terpentine oils, higher alcohols, preferably C8 to C10 alcohols, terpene alcohols or de-aerating agents based on mineral and/or silicone oils, in particular commercial formulations of about 15 to 25% by weight of a mixture of mineral oil and silicone oil and about 75 to 85% by weight of a C8 alcohol, for example 2-ethyl-n-hexanol. These are usually used in amounts of 0.01 to 5% by weight based on the total weight of the ink.
The inks can be prepared in the customary manner by mixing the individual constituents into the desired amount of water. If necessary, the inks are clarified by filtration through an extra-fine filter.
The inks according to the invention are suitable, for example, for printing. Examples of appropriate printing processes are conventional printing, screen printing and inkjet printing processes.
The inks according to the invention are particularly suitable for use in recording systems of a type in which an ink is pressed out of a small opening in the form of droplets directed against a substrate on which an image is formed. Suitable substrates are, for example, textile fibre materials, paper or films of plastic. Suitable recording systems are, for example, commercially available ink-jet printers for use in printing of paper or textiles, or writing implements, such as fountain pens or ball-point pens, and in particular ink-jet printers.
It may be necessary, for example, to adjust the viscosity or other physical properties of the ink, in particular those which have an influence on the affinity for the particular substrate, according to the method of use.
The inks according to the invention which comprise dyes with fibre-reactive radicals are thus suitable for use in the printing of paper or textiles.
Inks which comprise dyes without fibre-reactive radicals are particularly suitable for recording on paper, and especially for use in the printing of paper.
Textile fibre materials are, in particular, fibre materials containing nitrogen or containing hydroxyl groups, for example textile fibre materials of cellulose, silk, wool or synthetic polyamides.
Examples of paper which can be printed with the inks according to the invention are commercially available ink-jet paper, photographic paper, glazed paper and paper coated with plastic, for example Epson Ink-Jet Paper, Epson Photo Paper, Epson Glossy Film, HP Special Ink Jet Paper, Encad Photo Gloss Paper and IIford Photo Paper. Films of plastic which can be printed with the inks according to the invention are, for example, transparent or milky/opaque. Suitable films of plastic are, for example, 3M Transparency-Film.
The present invention thus also relates to a process for printing paper, films of plastic or textile fibre materials, in particular by the ink-jet printing process, which comprises using an aqueous ink which comprises
20 to 95% by weight of at least one dye (A) together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A),(B) and (C) in the ink, and
1 to 40% by weight of a water-miscible organic solvent , based on the total weight of the ink, wherein
the dyes (A), (B) and (C) are as defined and preferred above.
In the case of the ink-jet printing process, individual drops of the ink are sprayed out of a jet in a controlled manner onto a substrate. The continuous ink-jet method and the drop-on-demand method are chiefly used for this. In the case of the continuous ink-jet method, the drops are produced continuously, drops which are not required for printing being diverted into a collecting container and recycled. In the case of the drop-on-demand method, on the other hand, drops are produced and printed as required, i.e. drops are only produced if this is necessary for printing. The drops can be produced, for example, by means of a piezo ink-jet head or by means of thermal energy (bubble jet). Printing by means of a piezo ink-jet head is preferred for the process according to the invention. Printing by the continuous ink-jet method is furthermore preferred for the process according to the invention.
The records produced, such as, for example, prints, are distinguished by good black shades without a change in shade in artificial light (metamerism) with an outstanding fastness to light. Records which are produced with inks comprising a dye (A) together with a dye (C) show no xe2x80x9corange bleedingxe2x80x9d of the black shade.
The present invention also relates to black-dyeing dye mixtures which comprise 20 to 95% by weight of at least one dye (A) together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the dye mixture, where the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7), in which the radicals R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, B1, B2, B3, F1, F2, F3, A1, A2, A3, X1, X2, X3, X4, X5 and X6 are as defined and preferred above under the formulae (5), (6) and (7).
The dye mixtures according to the invention can be prepared, for example, by mixing the individual dyes. This mixing process is carried out, for example, in suitable mills, for example ball or pinned disc mills, and in kneaders or mixers.
The dye mixtures according to the invention in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7) and the radicals R10, R13 and R21; R11, R12, R15, R16, R19 and R20; R14, R17 and R18; B1, B2 and B3; F1, F2 and F3; A1, A2 and A3 and X1, X2, X3, X4, X5 and X6 in each case have identical meanings, can be prepared by reacting the compounds of the formulae (10a) and (10b)
F1xe2x80x94N(R10)Hxe2x80x83xe2x80x83(10a) 
and
A1xe2x80x94N(R14)Hxe2x80x83xe2x80x83(10b)
or corresponding dye intermediates, a halogenotriazine compound of the formula (11) 
and a diamine of the formula (12) 
in which A1, F1, R10, R11, R12 and R14 are as defined under the formulae (5) and (6), and X is halogen, for example fluorine or chlorine, with one another in any sequence and, in the case where dye intermediates are used, the resulting intermediate products are converted into the desired dyes, and, if appropriate, a further reaction with a compound of the formula (13)
Hxe2x80x94X1xe2x80x83xe2x80x83(13)
in which X1 is as defined under the formula (5), with the exception of halogen, follows.
The preparation of the end dyes from the intermediates is, in particular, coupling reactions which lead to azo dyes.
Since the individual process steps described above can be carried out in a different sequence, and in some cases also at the same time, if appropriate, various process variants are possible. In general, the reaction is carried out stepwise in succession, the sequence of the simple reactions between the individual reaction components advantageously depending on the particular conditions.
One process variant comprises reacting the compounds of the formulae (10a) and (10b) independently of one another with in each case an approximately equivalent amount of a halogenotriazine compound of the formula (11) to give the compounds of the formulae (14a) and (14b) 
and then subjecting a mixture of approximately two molar equivalents of the compounds of the formulae (14a) and (14b) to a condensation reaction with approximately one molar equivalent of a diamine of the formula (12) and, if appropriate, following this condensation step with a further reaction with a compound of the formula (13).
The ratio of the dyes of the formulae (5), (6) and (7) in the mixture can vary in the range stated and depends here on the ratio of the compounds of the formulae (14a) and (14b) in the reaction mixture.
The individual condensation reactions are carried out, for example, by processes which are known per se, as a rule in aqueous solution at a temperature of, for example, 0 to 50xc2x0 C. and a pH of, for example, 4 to 10.
The present invention relates to a process for the preparation of the dye mixtures according to the invention which do not comprise substantial amounts of a compound of the formula (6), which comprises
(i) reacting the compounds of the formulae (10a) and (10b) independently of one another with in each case a halogenotriazine compound of the formula (11) to give the compounds of the formulae (14a) and (14b),
(ii) reacting the compound of the formula (14b) with an excess of a diamine of the formula (12) such that a mixture of the compounds of the formulae (12) and (15) 
xe2x80x83is obtained,
(iii) subjecting this mixture to a condensation reaction with a compound of the formula (14a) in an equimolar amount which corresponds to the number of amino groups which have not been acylated by the compound of the formula (14b), to give a mixture of the compounds of the formulae (5a) and (7a) 
xe2x80x83and
(iv) if appropriate reacting the radicals X with a compound of the formula (13), in which A1, F1, R10, R11, R12 and R14 are as defined and preferred under the formulae (5) and (6), X is halogen, for example fluorine or chlorine, and X1 is as defined and preferred under the formula (5), and is not halogen.
The ratio of the dyes of the formulae (5a) and (7a) in the mixture can vary in the range stated and depends here on the ratio of the compounds of the formulae (12) and (14b) according to process step (ii), the molar ratio of the compounds of the formulae (12) and (14b) being greater than 1 and, for example, 1.5 to 10, and preferably 2 to 6. Process step (ii) is advantageously carried out at a pH of 5 to 7.
The compounds of the formulae (10a), (10b), (12) and (13) are known or can be obtained analogously to known compounds.
The present invention furthermore relates to dyes of the formula (9) 
in which
R23 is as defined and preferred for R10, R13, R14, R17, R18 and R21,
R24 and R25 independently of one another are as defined and preferred for R11, R12, R15, R16,
R19 and R20,
B4 is as defined and preferred for B1, B2 and B3,
A4 is a radical of the formula (VIII),
F4 is as defined and preferred for F1, F2 and F3 and
X7 is as defined and preferred for X1, X2, X3, X4, X5 and X6.
Dyes of the formula (9) can be prepared by an addition reaction of a compound of the formula (16) 
with a compound of the formula (17) 
in which the radicals R23, R24, R25, B4, F4 and W are as defined and preferred above and X is halogen, for example fluorine or chlorine, in the presence of a base, for example an alkali metal hydroxide, in particular sodium hydroxide, at a pH of, for example, 7 to 12, preferably 8 to 10.
If appropriate, the radical X7 can be introduced by first reacting the compound of the formula (16) or the resulting addition product of the compounds of the formulae (16) and (17) with a compound of the formula Hxe2x80x94X7, in which X7 is as defined and preferred, with the exception of halogen, by processes known per se.
The compounds of the formula (16) and (17) are known or can be prepared by processes known per se.
The present invention also relates to dyes (C) of the formula (18) 
in which
R26, R27, R28 and R29 independently of one another are hydrogen or substituted or unsubstituted C1-C4alkyl,
B5 is an aromatic bridge member and
F5 is a radical of the formula (I), (II), (III), (IVa), (IVb) or (IVc), in particular (I.1), (I.2), (I.3) (I.4), (I.5), (II.1), (II.2), (II.3), (III.1), (IVb) or (IVc),
A4 is a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j), (4k), (4l), (4m), (4n), (4o), (4p), (4q), (4r), (V), (VI) or (VII), preferably (4a), (4d), (4e), (4o), (4p), (4q), (4r), (V), (VI) or (VII), and in particular (4e), (4o), (4p), (4q), (V), (VI) or (VII), and
X8 and X9 are as defined and preferred above for X1, X2, X3, X4, X5 and X6.
R26 and R29 are as defined and preferred above for R10, R13, R14, R17, R18 and R21.
R27 and R28 are as defined and preferred above for R11, R12, R15, R16, R19 and R20.
A4 is as defined and preferred above for radicals A1, A2 and A3 of the formulae (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j), (4k), (41), (4m), (4n), (4o), (4p), (4q), (4r), (V), (VI) and (VII).
B5 is as defined and preferred above for aromatic bridge members B1, B2 and B3.
F5 is as defined and preferred above for radicals F1, F2 and F3 of the formulae (I), (II), (III), (IVa), (IVb) and (IVc).
The present invention also relates to dyes (C) of the formula (18) in which
R26, R27, R28 and R29 are as defined and preferred above,
B5 is an aliphatic bridge member,
F5 is as defined and preferred above,
A4 is a radical of the formula (4o) 
xe2x80x83in which
(R1)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, halogen, carboxyl and sulfo, in particular a sulfo group,
(R1xe2x80x2)0-3 is 0 to 3 identical or different substituents from the group consisting of C1-C4alkyl, C1-C4alkoxy, halogen, carboxyl and sulfo, in particular a sulfo group,
(R2)0-3 is 0 to 3 identical or different substituents from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4alkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, amino, C2-C4alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C1-C4alkylsulfonylamino and sulfo, in particular halogen, C1-C4alkyl, C1-C4alkoxy which is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, amino, C2-C4alkanoylamino, ureido, C1-C4alkylsulfonylamino and sulfo, and
Z is vinyl or a radical xe2x80x94CH2-CH2xe2x80x94U and U is a leaving group, and
X8 and X9 are as defined and preferred above.
The radical A4 preferably contains no fibre-reactive group of the formula xe2x80x94SO2xe2x80x94Z.
B5 is as defined and preferred above for aliphatic bridge members B1, B2 and B3.
The dyes of the formula (18) according to the invention can be prepared by processes known per se, such as are described, for example, in U.S. Pat. No. 5,684,138.
The invention also relates to a process for dyeing or printing fibre materials containing hydroxyl groups or containing nitrogen with the dyes or dye mixtures according to the invention.
Fibre materials are, for example, the natural cellulosic fibres, such as cotton, linen, jute or hemp, and modified cellulosic fibres, such as cellulose or regenerated cellulose. The dyes and dye mixtures according to the invention are also suitable for dyeing or printing natural polyamide fibre materials, for example silk or wool, synthetic polyamide fibre materials, for example polyamide 6 or polyamide 6.6, or wool and synthetic polyamide blend fabrics. The dyes and dye mixtures according to the invention are particularly suitable for dyeing or printing natural polyamide fibre materials, and here in particular wool or chlorinated wool or wool with a washing machine-resistant finish.
The textile fibre materials mentioned can be in the most diverse forms of processing here, for example as fibre, yarn, fluff, woven fabric or knitted fabric.
The dyes and dye mixtures according to the invention are suitable for customary dyeing and printing processes and can be applied and fixed to the fibre material in the most diverse ways, in particular in the form of aqueous dye solutions or printing pastes. They are suitable both for the exhaust method and for pad dyeing, in which the goods are impregnated with aqueous dye solutions, which may contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, with the action of heat if appropriate. The dyes and dye mixtures according to the invention are also suitable for the so-called cold pad-batch process, in which the dye is applied on the padder together with the alkali and is then fixed by storage at room temperature for several hours.
Dyeing of natural and synthetic polyamide fibre materials, in particular wool, is preferably carried out by the exhaust method at a pH of about 3 to 7, in particular 4 to 6, and at temperatures of, for example, 70 to 120xc2x0 C., and in particular 90 to 105xc2x0 C.
In addition to water and the dyes or dye mixtures according to the invention, the dye liquors or printing pastes can comprise further additives, for example shading dyes, salts, buffer substances, wetting agents, antifoams, levelling agents or agents which influence the properties of the textile material, for example softening agents, additives for a flame-retardant finish or soil-, water- and oil-repellent agents, as well as water-softening agents and natural or synthetic thickeners, for example alginates or cellulose ethers, these additives being known per se.
The dyes and dye mixtures according to the invention give level dyeings and prints with good allround properties, in particular good fastness to washing, rubbing, wet processing, wet rubbing and light. The dyes and dye mixtures according to the invention are furthermore distinguished by a uniform colour build-up, good affinity and high degrees of fixing. Furthermore, the otherwise customary after-treatment of the dyeings and prints with so-called fixing agents can be omitted in the case of the dyes and dye mixtures according to the invention.
The dye mixtures according to the invention in which the dye (A) has the formula (5), the dye (B) has the formula (6) and the dye (C) has the formula (7) and the dyes according to the invention has the formula (9) and (18) are furthermore distinguished by a good solubility.